Printing paste and method of printing textiles therewith



United States Patent PRINTING PASTE AND METHOD OF PRINTING TEXTILES THEREWITH- Helmut Kleiner, Opladen, and WolfgangLhmanm'IJeverkusen-Bayerwerk, Germany, assignors to Farb'enfabriken Bayer Aktiengesellsch'aft, 'Leverkusen, Germany, a corporation-of Germany No Drawingf Application July 22, 1952,

Serial No. 300,339

8 Claims. .(Cl. 117-38) The present invention relates "to a new process of decorating substrata, especially textile fabrics.

It has heretofore been proposed to insolubilize soluble or fusible compounds containing two or more primary or secondary amino groups in the mole'cule by'theaction of polyfunctional compounds which \arecapa'ble of reacting with amino. groups.

In accordance with the invention it has been found that insoluble coatings, for instance for fixation of pigments in textile printing, for producing films, for-impregnating and sizing, are obtained ;by using soluble or fusible substances, such as polymers, condensation or addition'products, containing in their molecule, 'on the one'hand, basic nitrogen groups 'capableof forming salts and, on the other hand, groups which are capable "of reacting with the basic nitrogen groups with cross lirikmg.

The soluble or fusiblepolyrners employed accordingto this invention may contain side-chains in their molecule. The basic nitrogen groups may be primary, secondary or tertiary amino groups or qua-ternary ammoniu'rnlgroups;

As soluble -o'r fusible compounds polymers :may be employed containing recurringv groups of the general-formula L R R wherein X stan'dsfor "or O, Rsta'nds for H or a lower alkylradical such as CH3 C iIfIe, Gil-Ia, Gs'Hrs etc., q, r, s and 1 stand for an integer from lto about .8, m and nstan'dfor aniintegerjfrompfto about 2, and "p stands foran integerfro'm O to about 8.

Th'e b'asic pdlyaniides according to'theab'ove formula (X=,.NH) may be obtained by reactingpolyamin es, for instance diprimary polyamines such as die thyle'rie triamine, triethylene tetrami'ne, a,a'-diamino dipropyl diaminobutane zetc. with aliphatic dicarboxylic acids or the esters thereof, for instancecoxalic acid, succinic-acid and .sebacic acid.

The corresponding basic esters (-X== --O; are obtainalble-by -using 3arninoalcohols such as OH( CHQJQNH (CH2) 20H insteadofthe .polyamines in the above reaction.

Furthermore suitable compounds include polymers of the general formula:

radical, such as CH3, CzHs, Gil-I9 etc., q,'r, san'd t'sta'nd ice Among these products the basic polyureas are especially useful according to the invention. The

basic polyureas are formed by reacting diisocyanates with aliphatic polya'mines, preferably diprimary polyamines, in an alcoholic solution.

The basic urethanes (X=O-, 'Y=-NH- and either by reaction of aliphatic polyamines, preferably'diprimary polyamines, with bisalkyl-chloroformates or by reaction of N-acetyl-diethanol-amine with hexamethylene 'diisocyanate and subsequent splitting off of the actyl group.

5 tioned formulae are preferably so selected that the indices. p,-q, r, sand t do not substantially exceed the number, eight. i

Besides the above mentioned diprimary p'olyai'nines long chain compounds containing imino groups may be used which are obtainable by the addition of bifu nctional amines to acrylonitrile and subsequent'hydrogenw tion. These compounds may be linked to yield long chain compounds by reaction with diisocyanates, dicarbox-ylic acids or theiracid dichlorides, diacrylamides etc.

Forinstance aerylonitrile is added to hexame t hylene diarnine on both sides and hydrogenated. The addition of the reaction product to a further acrylonitrile molecule and subsequent hydrogenation is repeated several times until the desired product is obtained:

HzN (CH2 3- [NH( CH2 3 4N-HI(CH2) eNH E(CH2)3NH]4 --,(CH2)a.-NH2

This poly-base may be prolongedat the terminal amino groups by further reaction with bifunctional compounds, "for instance oxalyl chloride, phosgene, diisocyanates and diacrylamides (in this reaction the terminal -NHzgroup is added to the acrylic do uble bond).

Furthermore as examples ,of basic compounds according to fthe invention may be named basic polysaccharides, the so-called aminocellulose, amino-starch,

5 addition products of ethylene imino and. cellulose, derivatives of protein substances, for instance aminolysates and hydrolysates of glue, casein and gelatine.

The polymers to be used according to the invention are preferably applied in solution in order to inhibit a premature reaction of the amino groups with the other reactive substituents in themolecule. Itisof advantage to protect theamino groups by salt formation; Especially useful for this purpose are acids which are easily "valatile or can easily be separated at higher temperatures, for instance weak organic acids such as acetic acid and :lactic acid. In general the intermolecular crosslinkingqis ca'rriedout at temperatures from about to about 200 C. When strong acids are employed the methylene diisocyanate so that the content of free amino groups can be set free by an alkaline treatment N=C=O amounts to about 4.6%. Of the impregnated 01? dewffited material, instance a 100 parts of the above isocyanate modified polyester are printed fabric. In the latter case cross-linking may be di l d i effected at somewhat lower temperatures, say about 80 5 100 parts of benzene and gradually added with stirring to about 150 C.

The process of the invention may serve for various purposes, for instance for fixing pigments in textile 100 parts of benzene. g. for imliregnating for preparing .films or Coat' The paste is heated to the boil for /2 hour, the benzene ings, 512mg makmg E F of,texnles is distilled off and the residue neutralized with dilute The Present mvenmn 1S fmther Illustrated by the acetic acid. The paste is adjusted to a content of 40%. following examples without being restricted thereto, the The viscous Solution can be diluted with Water in an Parts bemg by Welght proportions. The content of basic, salt forming nitrogen Example 1 amounts to 1.4% calculated on the solid substance.

By applying the solution to a substratum, for instance a fabric, and heating to 130 C. for 30 minutes a rubberlike, water-insoluble coating is obtained. The content of basic nitrogen in the coating, which can be determined by titration, has been reduced to 0.2%.

We claim:

l. A printing paste consisting of an aqueous solution of a salt of (A) an acid and (B) a basic polymer containing recurring groups of the general formulae selected from the group consisting of (1) to 105 parts of N-methylpropylene diamine and A basic polyurea of the viscosity number z =l38, which is prepared from 0.2 mol of diethylene triarnine, 0.8 mol of y:y'-diaminodipropylmethylamine and 1.0 mol of heXarnethylene diisocyanate is used for printing fabrics of cotton and staple fiber in the following paste:

400 parts of a 10% acetic acid'solution of the basic polyurea, I 150 parts of a 15% paste of copper phthalocyamne, 550 parts of water.

wherein X stands for a radical selected from the group consisting of -NH and O-, R stands for a radical selected from the group consisting of hydrogen and a lower alkyl radical, q, r, s and 1 stand for an integer from 2 to 3, and p stands for an integerfrorn 0 to 4, and (2) By aftertreating the printing designs at 100 C. for 5 minutes they are highly resistant to light and washing.

Example 2 A basic polyurethane of the viscosity number 2 :70,

L R R which has been prepared from 1 mol of dipropylene 1 wherein X stands for a radical selected from the group triamine and 1 mol of butane-bis-alkylchloroforrnate is consisting of NH-, -0 and a CC linkage, Y

40 stands for a radical selected from the group consisting of NH and O-, only one of the radicals X and Y being -O-, R stands for a radical selected from the group consisting of hydrogen and a lower alkyl radical, q, r, s and t stand for an integer from 2 to 3, and u stands for an integer from 2 to 4, a thickening agent and a pigment.

2. A printing paste as claimed in claim 1 in which the acid is a weak and volatile acid.

3. A printing paste as claimed in claim 2 in which the polymer contains recurring groups of the formula employed in the following printing paste:

200 parts of a 40% acetic acid solution of the basic polyurethane,

parts of a 15% paste of copper phthalocyanine,

35 parts of tragacanth,

400 parts of water.

By heating the printed material to 130 C. for 10 minutes the print shows a uniform blue color and is extraordinarily fast to light and washing. 5o

wherein R stands for a radical selected from the group consisting of hydrogen and a lower alkyl radical, q, r, s and t stand for an integer from 2 to 3, and p stands for Example 3 A polyurea of the viscosity number zn==150, which has been prepared from 1 mol of 7.7 diaminodipropylmethylamine and 1 mol of hexamethylene diisocyanate, an integer from 2 t0 is used for impregnating textiles in form of a 10% acetic A Printing Paste as claimed in claim 2 in Which the acid aqueous solution. By heating the fabric to 145 C. p lymer contains recurring groups of the formula 7 L R R R r J I for some time a finish is obtained which is fast to washh r n R st nds r a r di a selected from the s p ing. consisting of hydrogen and a lower alkyl radical, q, r,; s

" and t stand for an integer from 2 to 3, and p stands for an integer from 2 to 4. 5. A printing paste as claimed in claim 2 in which, the polymer contains recurring groups of the formula Example 4 ,A polyester prepared from 3 mols of adipic acid, 1 mol of trimethylol propane and 3 mols of butylene glycol,

which has a molecular weight of about 1200 and a wherein R stands for a radical selected from the group hydroxyl number of about 100, is reacted with hexaconsisting of hydrogen and a lower alkyl radical, q, r, s

and t stand for an integer from 2 to 3, and u stands for an integer from to 4.

6. The process for printing textiles which comprises applying to said textiles an aqueous printing paste comprising a salt of (A) an acid and (B) a linear high molecular weight compound containing recurring groups of the general formulae selected from the group consisting of 1) lower alkyl radical, q, r, s and 1 stand for an integer from 2 to 3, and p stands for an integer from 0 to 4, and (2) wherein X stands for a radical selected from the group consisting of -NH and O-, R stands for a radical stands for a radical selected from the group consisting of NH- and -O, only one of the radicals X and Y being O-, R stands for a radical selected from the group consisting of hydrogen and a lower alkyl radical, q, r, s and t stand for an integer from 2 to 3, and it stands for an integer from 2 to 4, a thickening agent and a pigment, and then developing at temperatures from about 80 C. to about 200 C.

8. The process for printing textiles which comprises applying to said textiles an aqueous printing paste comprising a salt of (A) an acid and (B) a linear high molecular weight compound containing recurring groups of the general formulae selected from the group consisting of (1) wherein X stands for a radical selected from the group consisting of NH-, 0-- and a C--C linkage, Y

selected from the group consisting of hydrogen and a lower alkyl radical, q, r, s and I stand for an integer from 2 to 3, and p stands for an integer from 0 to 4, and (2) .J R R R wherein X stands for a radical selected from the group consisting of NH, --O- and a C-C linkage, Y

stands for a radical selected from the group consisting for an integer from 2 to 4, a thickening agent and a pigment, and then developing by treating the textiles with an alkaline medium selected from the group consisting of an aqueous solution of an alkali metal hydroxide,

7. The process as claimed in claim 6 wherein the acid 3 metal carbonate ammonia, and developing at is a weak and volatile acid. temperatures of about to about C.

References Cited in the file of this patent UNITED STATES PATENTS France June 16, 1943 

6. THE PROCESS FOR PRINTING TEXTILES WHICH COMPRISES APPLYING TO SAID TEXTILES AN AQUEOUS PRINTING PASTE COMPRISING A SALT OF (A) AN ACID AND (B) A LINEAR HIGH MOLECULAR WEIGHT COMPOUND CONTAINING RECURRING GROUPS OF THE GENERAL FORMULEA SELECTED FROM THE GROUP CONSISTING OF (1) 